CN115612252A - Formula of reactive flame-retardant epoxy resin and preparation method and application thereof - Google Patents
Formula of reactive flame-retardant epoxy resin and preparation method and application thereof Download PDFInfo
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- CN115612252A CN115612252A CN202211261491.6A CN202211261491A CN115612252A CN 115612252 A CN115612252 A CN 115612252A CN 202211261491 A CN202211261491 A CN 202211261491A CN 115612252 A CN115612252 A CN 115612252A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003063 flame retardant Substances 0.000 title claims abstract description 96
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 73
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 diethyl 12-mercapto dodecyl Chemical group 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 125000003944 tolyl group Chemical group 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the field of high polymer materials, in particular to a reactive flame-retardant epoxy resin formula and a preparation method and application thereof; the silsesquioxane flame retardant is quickly prepared by one-step method through the reaction of toluene, acrylic group-cage polysilsesquioxane, diethyl 12-mercapto dodecyl phosphate, triethylamine and benzoyl peroxide; then adding epoxy resin, and curing to obtain reactive flame-retardant epoxy resin; the flame-retardant element is combined into a macromolecular chain of the epoxy resin and becomes a chain link on the macromolecular chain of the high polymer, and the high flame retardance is displayed without precipitation; the resin has a lasting flame-retardant effect, and simultaneously, the original thermal properties, mechanical properties and the like of the resin are still maintained; the limit oxygen index of the reactive flame-retardant epoxy resin prepared by the invention reaches 34.0 percent and passes UL-94 testThe bending strength and the impact strength of the steel reach 107.2MPa and 24.5kJ/m 2 And the application range of the resin is widened.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a reactive flame-retardant epoxy resin formula and a preparation method and application thereof.
Background
The epoxy resin is an advanced composite material resin matrix which is generally applied at present, and the cured epoxy resin has the advantages of excellent bonding performance, mechanical strength, good electrical insulation and chemical stability, small curing shrinkage, good product size stability, easiness in molding and processing, good stress transferability, low cost and the like, and is widely applied to the fields of aerospace, electronics and electricity and the like. Because the epoxy resin has poor flame retardant property and the oxygen index is about 19.8, the epoxy resin is difficult to meet the requirements of special engineering technology, and the application of the epoxy resin in a plurality of important fields is limited, so that the epoxy resin is imperatively subjected to flame retardant modification. And with
Application number CN202110913010.4 discloses a reaction type flame-retardant epoxy resin curing agent and a preparation technology thereof, relating to the technical field of flame-retardant epoxy resin curing agents; the raw materials comprise: basic amine, epoxy resin, epoxy polyether at two ends, epoxy silicone oil at two ends, epoxy reactive diluent and deionized water; the preparation method comprises the following steps: adding basic amine into a reactor, heating the system under the condition of introducing nitrogen and stirring, adding epoxy resin, double-end epoxy polyether, double-end epoxy silicone oil and epoxy reactive diluent, and finally dropwise adding deionized water; and (2) carrying out phase inversion on the system to obtain a reactive flame-retardant epoxy resin curing agent emulsion, wherein the solid content of the obtained reactive flame-retardant epoxy curing agent is 65%, and after the curing agent is matched with standard liquid epoxy resin in an equivalent manner, a varnish film is burnt by a lighter at room temperature under the state specified by national standards: after ignition, the combustion time is not more than 5s, and the flame retardant effect is better.
Application number CN202110716028.5 relates to the field of organic intermediate synthesis and high molecular materials, in particular to a phosphorus-containing halogen-free flame-retardant epoxy resin, a preparation method thereof and an intrinsic flame-retardant transparent epoxy resin material. The invention provides a transparent halogen-free flame-retardant epoxy resin, which has a structural formula shown in a formula I, wherein R is a residue of-OH reaction in an epoxy resin and a flame retardant shown in a formula II. The flame-retardant epoxy resin with the new structure has the flame-retardant characteristic and the transparency, and can be prepared into an intrinsic flame-retardant transparent epoxy resin material.
Application number CN201810842354.9 discloses a novel P-N-Si synergistic flame-retardant epoxy resin curing agent, the molecular structural formula of which is shown as follows: the preparation raw materials comprise: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), dichlorodimethylsilane and p-aminophenol, wherein the preparation process of the flame retardant is carried out in two steps, firstly, the dichlorodimethylsilane and the p-aminophenol react to obtain an intermediate product, and then the intermediate product reacts with the DOPO to obtain a final product. The molecular structure contains three elements of P, N and Si, so that the flame retardant property of the cured epoxy resin is greatly improved.
In the above patents and the prior art, the flame retardant method of epoxy resin is mainly divided into two types, additive flame retardant and reactive flame retardant. The additive flame-retardant technology is characterized in that a substance with a flame-retardant effect is directly physically blended with the epoxy resin, the preparation process is simple, the flame retardant is diversified, but the problems of dispersibility, compatibility, interfacial property and the like of the flame retardant need to be solved, and the mechanical property of the epoxy resin is influenced to a great extent by the addition of the flame retardant.
Disclosure of Invention
Technical problem
The invention aims to provide an epoxy resin with a lasting flame-retardant effect and original thermal properties and mechanical properties of the resin, discloses a reactive flame-retardant epoxy resin formula and a preparation method and application thereof, and belongs to the field of high polymer materials.
Technical scheme
The first preferred embodiment of the present invention provides a process for preparing a reactive flame-retardant epoxy resin, which comprises the following steps:
weighing 85-100 parts of epoxy resin and 3-10 parts of silsesquioxane flame retardant according to the parts by mass, heating, stirring, adding 45-50 parts of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
As a further improvement of the invention, the reaction temperature is 95-110 ℃, and the reaction time is 3-6h.
As a further improvement of the invention, the stirring speed is 500-800 revolutions/min.
As a further improvement of the invention, the vacuum degree of the vacuum oven is-80 to-100 kpa, the temperature is 65-80 ℃, and the time is 6-10h.
As a further improvement of the invention, the curing agent is DDM.
As a further improvement of the invention, the curing procedure is to firstly heat up to 95-110 ℃ for curing for 1-3h, and then heat up to 140-160 ℃ for curing for 1-3h.
A second preferred embodiment of the present invention provides a process for preparing a silsesquioxane flame retardant:
weighing 150-170 parts of solvent, 17-22 parts of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8) and adding into a reactor, slowly dropping 10-16 parts of diethyl 12-mercaptododecyl phosphate, 3-6 parts of triethylamine and 0.8-2.1 parts of benzoyl peroxide, and heating for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
As a further development of the invention, the solvent is toluene.
As a further improvement of the invention, the reaction temperature is 85-100 ℃, and the reaction time is 3-6h.
As a further improvement of the invention, the evaporation temperature is controlled to be 120-135 ℃.
Technical innovation
The acrylate group-cage polysilsesquioxane and diethyl 12-mercapto dodecyl phosphate ester are subjected to mercapto Michael addition reaction to obtain the silsesquioxane modified phosphate ester flame retardant, so that the flame retardance of the epoxy resin is effectively improved.
Advantageous effects
Compared with the prior art, the reactive flame-retardant epoxy resin formula, the preparation method and the application thereof have the following remarkable advantages:
1. the flame-retardant element is combined into a macromolecular chain of the epoxy resin and becomes a chain link on the macromolecular chain of the high polymer, and the high flame retardance is displayed without precipitation; the resin has a lasting flame-retardant effect, and simultaneously, the original thermal properties, mechanical properties and the like of the resin are still maintained;
2. the limit oxygen index of the prepared reactive flame-retardant epoxy resin reaches 34.0 percent, and the bending strength and the impact strength of the reactive flame-retardant epoxy resin reach 107.2MPa and 24.5kJ/m through the V-0 grade tested by UL-94 2 The application range of the resin is widened, and the resin has important practical application value.
Drawings
FIG. 1 is a graph of heat release rate over time for examples 1-4, and a blank.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
The experimental procedures in the following examples are all conventional ones unless otherwise specified. The raw materials and reagent materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 85g of epoxy resin and 3g of silsesquioxane flame retardant, heating, stirring, adding 45g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 95 ℃, and the reaction time is 3h.
The stirring rate was 500 rpm.
The vacuum degree of the vacuum oven is-80 kpa, the temperature is 65 ℃, and the time is 6 hours.
The curing agent is DDM.
The curing procedure is that the temperature is firstly increased to 95 ℃ for curing for 1h, and then the temperature is increased to 140 ℃ for curing for 1h.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
150g of solvent and 17g of acrylic acid group-cage polysilsesquioxane (CAS: 1620202-27-8) are weighed and added into a reactor, 10g of diethyl 12-mercaptododecyl phosphate, 3g of triethylamine and 0.8g of benzoyl peroxide are slowly dropped into the reactor, and the temperature is raised for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 85 ℃, and the reaction time is 3h.
Example 2
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof, the operation steps are as follows:
weighing 90g of epoxy resin and 5g of silsesquioxane flame retardant, heating, stirring, adding 46g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 100 ℃, and the reaction time is 4h.
The stirring rate was 600 revolutions per minute.
The vacuum degree of the vacuum oven is-90 kpa, the temperature is 70 ℃, and the time is 7 hours.
The curing agent is DDM.
The curing procedure is that the temperature is firstly increased to 100 ℃ for curing for 2h, and then the temperature is increased to 145 ℃ for curing for 2h.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
155g of solvent and 19g of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8) are weighed and added into a reactor, 12g of diethyl 12-mercapto dodecyl phosphate, 4g of triethylamine and 1g of benzoyl peroxide are slowly dropped, and the temperature is raised for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 90 ℃, and the reaction time is 4h.
Example 3
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 95g of epoxy resin and 8g of silsesquioxane flame retardant, heating, stirring, adding 48g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 105 ℃, and the reaction time is 5h.
The stirring rate was 700 rpm.
The vacuum degree of the vacuum oven is-90 kpa, the temperature is 75 ℃, and the time is 9 hours.
The curing agent is DDM.
The curing procedure is that the temperature is firstly increased to 105 ℃ for curing for 2h, and then the temperature is increased to 155 ℃ for curing for 2h.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
weighing 165g of solvent and 21g of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8), adding into a reactor, slowly dropwise adding 14g of diethyl 12-mercaptododecyl phosphate, 5g of triethylamine and 1.5g of benzoyl peroxide, and heating for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 95 ℃, and the reaction time is 5h.
Example 4
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 100g of epoxy resin and 10g of silsesquioxane flame retardant, heating, stirring, adding 50g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 110 ℃, and the reaction time is 6h.
The stirring rate was 800 revolutions/min.
The vacuum degree of the vacuum oven is-100 kpa, the temperature is 80 ℃, and the time is 10 hours.
The curing agent is DDM.
The curing procedure is that the temperature is firstly increased to 110 ℃ for curing for 3h, and then the temperature is increased to 160 ℃ for curing for 3h.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
170g of solvent and 22g of acrylic acid based cage polysilsesquioxane (CAS: 1620202-27-8) are weighed and added into a reactor, 16g of diethyl 12-mercapto dodecyl phosphate, 6g of triethylamine and 2.1g of benzoyl peroxide are slowly dropped into the reactor, and the temperature is raised for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 100 ℃, and the reaction time is 6h.
Comparative example 1
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 85g of epoxy resin and 3g of silsesquioxane flame retardant, heating, stirring, adding 45g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 95 ℃, and the reaction time is 3h.
The stirring rate was 500 rpm.
The vacuum degree of the vacuum oven is-80 kpa, the temperature is 65 ℃, and the time is 6 hours.
The curing agent is DDM.
The curing procedure is to heat up to 95 ℃ for curing for 1 hour, and then heat up to 140 ℃ for curing for 1 hour.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
weighing 150g of solvent and 17g of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8), adding into a reactor, slowly dropping 3g of triethylamine and 0.8g of benzoyl peroxide, and heating for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 85 ℃, and the reaction time is 3h.
Comparative example 2
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 85g of epoxy resin and 3g of silsesquioxane flame retardant, heating, stirring, adding 45g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 95 ℃, and the reaction time is 3h.
The stirring rate is 500 revolutions per minute.
The vacuum degree of the vacuum oven is-80 kpa, the temperature is 65 ℃, and the time is 6 hours.
The curing agent is DDM.
The curing procedure is to heat up to 95 ℃ for curing for 1 hour, and then heat up to 140 ℃ for curing for 1 hour.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
weighing 150g of solvent and 17g of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8), adding into a reactor, slowly dropwise adding 10g of diethyl 12-mercaptododecyl phosphate and 3g of triethylamine, and heating for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 85 ℃, and the reaction time is 3h.
Comparative example 3
A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 85g of epoxy resin and 3g of silsesquioxane flame retardant, heating, stirring, adding 45g of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
The reaction temperature is 95 ℃, and the reaction time is 3h.
The stirring rate is 500 revolutions per minute.
The vacuum degree of the vacuum oven is-80 kpa, the temperature is 65 ℃, and the time is 6 hours.
The curing agent is DDM.
The curing procedure is that the temperature is firstly increased to 95 ℃ for curing for 1h, and then the temperature is increased to 140 ℃ for curing for 1h.
The preparation method of the silsesquioxane flame retardant comprises the following steps:
150g of solvent and 17g of acrylic group-cage polysilsesquioxane (CAS: 1620202-27-8) are weighed and added into a reactor, 10g of diethyl 12-mercaptododecyl phosphate and 0.8g of benzoyl peroxide are slowly dropped into the reactor, and the temperature is raised for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
The solvent is toluene.
The reaction temperature is 85 ℃, and the reaction time is 3h.
EXAMPLES evaluation of resin Properties
1. Testing Limit Oxygen Index (LOI) by adopting HC-2C type oxygen index tester produced by Nanjing Jiangning analytical instrument factory according to GB/T2406.2-2009 standard, wherein the sample size is 130 multiplied by 6.5 multiplied by 3.2mm3;
2. the impact strength was measured according to GB/T1043.1-2008 using a ZBC1251 pendulum impact tester manufactured by SANS corporation, with a specimen size of 80X 10X 4mm3;
3. the bending properties were tested in accordance with GB/T9341-2008 using a universal testing machine model CMT4104 manufactured by SANS, with a loading speed of 2mm/min and a specimen size of 80X 10X 4mm3.
Each sample was tested for 5 specimens above and the average was taken.
The results of the performance tests of the above examples and comparative examples are shown in the following table:
the present invention has been described in conjunction with the specific embodiments and comparative examples described above, and many variations will become apparent to those skilled in the art upon review of the foregoing description. The scope of the present invention includes those variations that are within the scope of the claims of the present invention and the spirit thereof.
Claims (10)
1. A reactive flame-retardant epoxy resin formula, a preparation method and an application thereof are disclosed, and the preparation method comprises the following operation steps:
weighing 85-100 parts of epoxy resin and 3-10 parts of silsesquioxane flame retardant according to the parts by mass, heating, stirring, adding 45-50 parts of curing agent, removing bubbles in a vacuum oven, pouring into a preheated stainless steel mold, and putting into the oven for heating and curing; and after curing, cooling and demolding to obtain the reactive flame-retardant epoxy resin.
2. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the reaction temperature is 95-110 ℃, and the reaction time is 3-6h.
3. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the stirring speed is 500-800 r/min.
4. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the vacuum degree of the vacuum oven is-80 to-100 kpa, the temperature is 65-80 ℃, and the time is 6-10 hours.
5. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the curing agent is DDM.
6. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the curing procedure is to heat to 95-110 ℃ for curing for 1-3h and then heat to 140-160 ℃ for curing for 1-3h.
7. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 1 are characterized in that: the preparation method of the silsesquioxane flame retardant comprises the following steps:
weighing 150-170 parts of solvent and 17-22 parts of acrylic group-cage polysilsesquioxane according to the mass parts, adding into a reactor, slowly dripping 10-16 parts of diethyl 12-mercapto dodecyl phosphate, 3-6 parts of triethylamine and 0.8-2.1 parts of benzoyl peroxide, and heating for reaction; and after the reaction is finished, carrying out suction filtration, evaporating to remove the solvent, and carrying out vacuum drying to obtain the silsesquioxane flame retardant.
8. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 7 are characterized in that: the solvent is toluene.
9. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 7 are characterized in that: the reaction temperature is 85-100 ℃, and the reaction time is 3-6h.
10. The formula, the preparation method and the application of the reactive flame-retardant epoxy resin according to claim 7 are characterized in that: the evaporation temperature is controlled between 120 and 135 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008024894A (en) * | 2006-07-25 | 2008-02-07 | Sekisui Chem Co Ltd | Thermosetting resin composition and electronic equipment |
| CN104262538A (en) * | 2014-09-23 | 2015-01-07 | 厦门大学 | Phosphorus/silicon-containing reactive high-molecular flame retardant, and preparation method and application thereof |
| CN104845049A (en) * | 2015-06-05 | 2015-08-19 | 厦门大学 | Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material |
| CN105315492A (en) * | 2015-12-04 | 2016-02-10 | 南昌航空大学 | Phosphorus silicon boron fire retardant based on cage-shaped silsesquioxane and preparation method thereof |
| CN106750239A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of phosphorus-nitrogen containing fluoropolymer fire retardant and preparation method and application |
| CN106750328A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine silicon polyphosphate and its preparation method and application |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
| CN110294846A (en) * | 2018-03-21 | 2019-10-01 | 中国科学院化学研究所 | A kind of cage web frame of the group containing DOPO mixes silsesquioxane fire retardant and the preparation method and application thereof |
-
2022
- 2022-10-14 CN CN202211261491.6A patent/CN115612252B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008024894A (en) * | 2006-07-25 | 2008-02-07 | Sekisui Chem Co Ltd | Thermosetting resin composition and electronic equipment |
| CN104262538A (en) * | 2014-09-23 | 2015-01-07 | 厦门大学 | Phosphorus/silicon-containing reactive high-molecular flame retardant, and preparation method and application thereof |
| CN104845049A (en) * | 2015-06-05 | 2015-08-19 | 厦门大学 | Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material |
| CN105315492A (en) * | 2015-12-04 | 2016-02-10 | 南昌航空大学 | Phosphorus silicon boron fire retardant based on cage-shaped silsesquioxane and preparation method thereof |
| CN106750239A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of phosphorus-nitrogen containing fluoropolymer fire retardant and preparation method and application |
| CN106750328A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine silicon polyphosphate and its preparation method and application |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
| CN110294846A (en) * | 2018-03-21 | 2019-10-01 | 中国科学院化学研究所 | A kind of cage web frame of the group containing DOPO mixes silsesquioxane fire retardant and the preparation method and application thereof |
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